TWI699160B - Shielding film and shielding printed circuit board - Google Patents

Shielding film and shielding printed circuit board Download PDF

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Publication number
TWI699160B
TWI699160B TW105116308A TW105116308A TWI699160B TW I699160 B TWI699160 B TW I699160B TW 105116308 A TW105116308 A TW 105116308A TW 105116308 A TW105116308 A TW 105116308A TW I699160 B TWI699160 B TW I699160B
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Taiwan
Prior art keywords
shielding film
conductive adhesive
parts
weight
adhesive layer
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TW105116308A
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Chinese (zh)
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TW201707552A (en
Inventor
高見晃司
山本祥久
上農憲治
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日商拓自達電線股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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    • H—ELECTRICITY
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    • C09J2301/314—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive layer and/or the carrier being conductive
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/10—Presence of inorganic materials
    • C09J2400/16—Metal
    • C09J2400/163—Metal in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2453/00—Presence of block copolymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2463/00—Presence of epoxy resin
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
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  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Soil Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
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Abstract

本發明提供一種同時滿足優異之高速傳送特性與優異之阻燃性之屏蔽薄膜。根據本發明之實施形態之屏蔽薄膜，具備金屬層、及配置於金屬層之一側之導電性接著劑層。導電性接著劑層包含環氧樹脂與含羧基之彈性體之硬化物、有機磷系阻燃劑及導電性填料。金屬層之厚度為0.3μm~7μm。構成導電性接著劑層之導電性接著劑，相對於環氧樹脂及含羧基之彈性體之合計100重量份，含有10重量份~50重量份之有機磷系阻燃劑、及10重量份~80重量份之導電性填料。 The present invention provides a shielding film that satisfies both excellent high-speed transmission characteristics and excellent flame retardancy. The shielding film according to the embodiment of the present invention includes a metal layer and a conductive adhesive layer arranged on one side of the metal layer. The conductive adhesive layer includes a cured product of an epoxy resin and a carboxyl group-containing elastomer, an organic phosphorus flame retardant, and a conductive filler. The thickness of the metal layer is 0.3μm~7μm. The conductive adhesive constituting the conductive adhesive layer contains 10 parts by weight to 50 parts by weight of the organophosphorus flame retardant, and 10 parts by weight relative to 100 parts by weight of the total of epoxy resin and carboxyl group-containing elastomer. 80 parts by weight of conductive filler.

Description

屏蔽薄膜及屏蔽印刷電路板 Shielding film and shielding printed circuit board

本發明關於屏蔽薄膜及屏蔽印刷電路板。 The present invention relates to a shielding film and a shielding printed circuit board.

背景技術 Background technique

已知有為遮蔽自印刷電路板產生之電磁波雜訊或來自外部之電磁波雜訊，而於軟性印刷電路板之表面設置電磁波屏蔽薄膜(亦簡稱為屏蔽薄膜)。 It is known that in order to shield electromagnetic wave noise generated from the printed circuit board or electromagnetic wave noise from the outside, an electromagnetic wave shielding film (also referred to as a shielding film) is provided on the surface of the flexible printed circuit board.

近年來，因行動電子機器之高速傳送化，對使用於印刷電路板之材料要求優異之高速傳送特性、更詳細而言要求比介電常數及介電損失正切較低之特性。其結果，對屏蔽薄膜亦要求上述優異之高速傳送特性。另一方面，對屏蔽薄膜大多要求阻燃性。作為對屏蔽薄膜賦與阻燃性之技術，已知有於導電性接著劑使用無鹵素系阻燃劑(專利文獻1)。然而，經賦與阻燃性之屏蔽薄膜存在有比介電常數及介電損失正切在高速傳送化之要求程度上不足之問題。 In recent years, due to the high-speed transmission of mobile electronic devices, materials used in printed circuit boards are required to have excellent high-speed transmission characteristics, and more specifically, characteristics that are lower than dielectric constant and dielectric loss tangent. As a result, the above-mentioned excellent high-speed transmission characteristics are also required for the shielding film. On the other hand, flame retardancy is often required for shielding films. As a technique for imparting flame retardancy to a shielding film, it is known that a halogen-free flame retardant is used for a conductive adhesive (Patent Document 1). However, the flame-retardant shielding film has the problem that the specific permittivity and the dielectric loss tangent are insufficient for high-speed transmission.

如上所述，強烈謀求同時滿足優異之高速傳送特性與優異之阻燃性之屏蔽薄膜。 As mentioned above, there is a strong demand for a shielding film that meets both excellent high-speed transmission characteristics and excellent flame retardancy.

先行技術文獻 Advanced technical literature 專利文獻 Patent literature

專利文獻1：日本特開2007-294918號公報 Patent Document 1: Japanese Patent Application Publication No. 2007-294918

發明概要 Summary of the invention

本發明是為解決上述先前問題而完成者，其目的在於提供一種同時滿足優異之高速傳送特性與優異之阻燃性之屏蔽薄膜。 The present invention was completed in order to solve the aforementioned problems, and its object is to provide a shielding film that satisfies both excellent high-speed transmission characteristics and excellent flame retardancy.

本發明之屏蔽薄膜具備金屬層、及配置於該金屬層之一側之導電性接著劑層。該導電性接著劑層包含環氧樹脂與含羧基之彈性體之硬化物、有機磷系阻燃劑及導電性填料。金屬層之厚度為0.3μm~7μm。構成導電性接著劑層之導電性接著劑，相對於環氧樹脂及含羧基之彈性體之合計100重量份，含有10重量份~50重量份之有機磷系阻燃劑、及10重量份~80重量份之導電性填料。 The shielding film of the present invention includes a metal layer and a conductive adhesive layer arranged on one side of the metal layer. The conductive adhesive layer includes a cured product of an epoxy resin and a carboxyl group-containing elastomer, an organic phosphorus flame retardant, and a conductive filler. The thickness of the metal layer is 0.3μm~7μm. The conductive adhesive constituting the conductive adhesive layer contains 10 parts by weight to 50 parts by weight of the organophosphorus flame retardant, and 10 parts by weight relative to 100 parts by weight of the total of epoxy resin and carboxyl group-containing elastomer. 80 parts by weight of conductive filler.

於一實施形態中，上述含羧基之彈性體為經以不飽和羧酸改性之苯乙烯-乙烯丙烯-苯乙烯共聚物。 In one embodiment, the above-mentioned carboxyl group-containing elastomer is a styrene-ethylene propylene-styrene copolymer modified with an unsaturated carboxylic acid.

於一實施形態中，上述有機磷系阻燃劑為次膦酸金屬鹽。 In one embodiment, the organic phosphorus flame retardant is a metal phosphinate.

於一實施形態中，上述導電性接著劑層具有VTM-0或較其良好之阻燃性，且於1GHz下具有2.0~4.0之比介電常數及0.0015~0.0040之介電損失正切。 In one embodiment, the conductive adhesive layer has VTM-0 or better flame retardancy, and has a specific dielectric constant of 2.0 to 4.0 and a dielectric loss tangent of 0.0015 to 0.0040 at 1 GHz.

根據本發明之另一態樣，可提供一種屏蔽印刷電路 板。該屏蔽印刷電路板包含上述屏蔽薄膜。 According to another aspect of the present invention, a shielded printed circuit can be provided board. The shielding printed circuit board includes the above-mentioned shielding film.

根據本發明之實施形態，藉由於屏蔽薄膜之導電性接著劑層中組合使用特定之硬化性樹脂(結果為硬化物)與有機磷系阻燃劑，可獲得同時滿足優異之高速傳送特性(主要為低的比介電常數及介電損失正切)與優異之阻燃性之屏蔽薄膜。 According to the embodiment of the present invention, by combining a specific curable resin (resulting in a cured product) and an organophosphorus flame retardant in the conductive adhesive layer of the shielding film, it is possible to obtain excellent high-speed transmission characteristics (mainly It is a shielding film with low specific dielectric constant and dielectric loss tangent) and excellent flame retardancy.

10‧‧‧金屬層 10‧‧‧Metal layer

20‧‧‧導電性接著劑層 20‧‧‧Conductive adhesive layer

30‧‧‧保護層 30‧‧‧Protection layer

40‧‧‧離型薄膜 40‧‧‧Release film

100‧‧‧屏蔽薄膜 100‧‧‧Shielding film

圖1是本發明之一實施形態之屏蔽薄膜之概略剖面圖。 Fig. 1 is a schematic cross-sectional view of a masking film according to an embodiment of the present invention.

圖2是比較顯示實施例2及參考例1之屏蔽薄膜之特性阻抗之曲線圖。 2 is a graph showing the characteristic impedance of the shielding film of Example 2 and Reference Example 1 in comparison.

圖3是比較顯示實施例2及參考例1之屏蔽薄膜之眼圖之像圖。 3 is an image diagram showing the eye diagrams of the shielding films of Example 2 and Reference Example 1 in comparison.

用以實施發明之形態 The form used to implement the invention

以下就本發明之具體實施形態進行說明，但本發明並不限定於其等實施形態。 Hereinafter, specific embodiments of the present invention will be described, but the present invention is not limited to these embodiments.

A.屏蔽薄膜之整體構成 A. The overall composition of the shielding film

圖1是本發明之一實施形態之屏蔽薄膜之概略剖面圖。本實施形態之屏蔽薄膜100具備金屬層10、及配置於金屬層10之一側之導電性接著劑層20。屏蔽薄膜100視需要亦可進一步具備配置於金屬層10之與導電性接著劑層20成相反之側之保護層30。於實用上，於金屬層10(保護層30存在 時為保護層30)之外側及/或導電性接著劑層20之外側，可剝離地暫時接著有離型薄膜(隔片)40，在提供給使用之前之期間保護屏蔽薄膜。 Fig. 1 is a schematic cross-sectional view of a masking film according to an embodiment of the present invention. The shielding film 100 of this embodiment includes a metal layer 10 and a conductive adhesive layer 20 arranged on one side of the metal layer 10. The shielding film 100 may further include a protective layer 30 disposed on the side of the metal layer 10 opposite to the conductive adhesive layer 20 as needed. Practically, in the metal layer 10 (the protective layer 30 exists When it is the outer side of the protective layer 30) and/or the outer side of the conductive adhesive layer 20, a release film (separator) 40 is temporarily attached in a peelable manner to protect the shielding film before being provided for use.

B.金屬層 B. Metal layer

金屬層10為包含金屬薄膜之層。金屬層10可作為電磁波屏蔽層而起作用。 The metal layer 10 is a layer including a metal thin film. The metal layer 10 can function as an electromagnetic wave shielding layer.

作為構成金屬層之金屬材料，例如可列舉：鋁、銀、銅、金、鎳、錫、鈀、鉻、鈦、及鋅、或包含其等二個以上之合金。金屬材料可視所期望之屏蔽特性而適當地選擇。 Examples of the metal material constituting the metal layer include aluminum, silver, copper, gold, nickel, tin, palladium, chromium, titanium, and zinc, or an alloy containing two or more of them. The metal material can be appropriately selected depending on the desired shielding characteristics.

於一實施形態中，作為金屬層可使用金屬箔。於此實施形態中，金屬層可藉由軋延加工形成為任意之厚度。於其他實施形態中，金屬層可藉由任意之適當方法而形成。作為形成方法之具體例，可列舉：物理性蒸鍍(真空蒸鍍、濺鍍、離子束蒸鍍等)、CVD、鍍敷。以物理性蒸鍍為佳。其原因為：可減薄厚度，且即使減薄厚度亦可於面方向賦與優異之導電性，可以乾式製程簡便地形成。於此實施形態中，金屬層在屏蔽薄膜設置有後述之保護層時，可藉由塗佈法將保護層形成於該金屬層上。 In one embodiment, a metal foil can be used as the metal layer. In this embodiment, the metal layer can be formed to any thickness by rolling. In other embodiments, the metal layer can be formed by any appropriate method. Specific examples of the formation method include physical vapor deposition (vacuum vapor deposition, sputtering, ion beam vapor deposition, etc.), CVD, and plating. Physical vapor deposition is better. The reason is that the thickness can be reduced, and even if the thickness is reduced, excellent conductivity can be imparted in the surface direction, and the dry process can be easily formed. In this embodiment, when the metal layer is provided with a protective layer described later on the shielding film, the protective layer can be formed on the metal layer by a coating method.

金屬層之厚度宜為7μm以下，較佳為0.3μm~7μm，更佳為1μm~6μm，尤佳為2μm~6μm。若金屬層之厚度為7μm以下，可經濟的製造輕量薄型之屏蔽薄膜。又，若金屬層之厚度為0.3μm以上，則後述傳送特性變得良好。金屬層之厚度若於此範圍，藉由與後述之導電性 接著劑層之效果之相乘效果，於所獲得之屏蔽薄膜可兼具優異之高速傳送特性與阻燃性。 The thickness of the metal layer is preferably 7 μm or less, preferably 0.3 μm to 7 μm, more preferably 1 μm to 6 μm, and particularly preferably 2 μm to 6 μm. If the thickness of the metal layer is less than 7μm, a lightweight and thin shielding film can be manufactured economically. In addition, if the thickness of the metal layer is 0.3 μm or more, the transmission characteristics described later become good. If the thickness of the metal layer is within this range, due to the conductivity described later The synergistic effect of the effect of the adhesive layer can combine excellent high-speed transmission characteristics and flame retardancy in the obtained shielding film.

金屬層之表面電阻宜為0.001Ω~1Ω，較佳為0.001Ω~0.1Ω。金屬層之表面電阻若於此範圍，可維持金屬層之屏蔽特性，且使金屬層成為上述所期望之厚度。 The surface resistance of the metal layer is preferably 0.001Ω~1Ω, preferably 0.001Ω~0.1Ω. If the surface resistance of the metal layer is within this range, the shielding characteristics of the metal layer can be maintained and the metal layer can be made to the desired thickness as described above.

C.導電性接著劑層 C. Conductive adhesive layer

導電性接著劑層20包含環氧樹脂與含羧基之彈性體之硬化物、有機磷系阻燃劑及導電性填料。換言之，導電性接著劑層20藉由使包含含有環氧樹脂及含羧基之彈性體之樹脂成分、有機磷系阻燃劑及導電性填料之導電性接著劑組成物硬化而形成。 The conductive adhesive layer 20 includes a cured product of an epoxy resin and a carboxyl group-containing elastomer, an organic phosphorus flame retardant, and a conductive filler. In other words, the conductive adhesive layer 20 is formed by curing a conductive adhesive composition including a resin component containing an epoxy resin and a carboxyl group-containing elastomer, an organic phosphorous flame retardant, and a conductive filler.

如上所述，導電性接著劑組成物包含含有環氧樹脂及含羧基之彈性體之樹脂成分、有機磷系阻燃劑及導電性填料。 As described above, the conductive adhesive composition includes a resin component containing an epoxy resin and a carboxyl group-containing elastomer, an organic phosphorus flame retardant, and a conductive filler.

作為環氧樹脂之具體例，可列舉：雙酚A型環氧樹脂、雙酚F型環氧樹脂或其等之氫化物；鄰苯二甲酸二縮水甘油酯、間苯二甲酸二縮水甘油酯、對苯二甲酸二縮水甘油酯、對羥基苯甲酸縮水甘油酯、四氫苯二甲酸二縮水甘油酯、琥珀酸二縮水甘油酯、己二酸二縮水甘油酯、癸二酸二縮水甘油酯、偏苯三酸三縮水甘油酯等縮水甘油酯系環氧樹脂；乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、1,4-丁二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、三羥甲基丙烷三縮水甘油醚、季戊四醇四縮水甘油醚、四苯基縮水甘油醚乙烷、三苯基縮水甘油醚乙烷、山梨糖醇之聚 縮水甘油醚、聚甘油之聚縮水甘油醚等縮水甘油醚系環氧樹脂；三縮水甘油基異氰尿酸酯、四縮水甘油基二胺基二苯基甲烷等縮水甘油胺系環氧樹脂；環氧化聚丁二烯、環氧化大豆油等線狀脂肪族環氧樹脂等。又，亦可使用苯酚型酚醛環氧樹脂、鄰甲酚酚醛環氧樹脂、雙酚A酚醛環氧樹脂等酚醛型環氧樹脂。進而，可使用溴化雙酚A型環氧樹脂、含磷之環氧樹脂、含二環戊二烯骨架之環氧樹脂、含萘骨架之環氧樹脂、蒽型環氧樹脂、第三丁基鄰苯二酚、三苯基甲烷型環氧樹脂、四苯基乙烷型環氧樹脂、聯苯型環氧樹脂、雙酚S型環氧樹脂等。 Specific examples of epoxy resins include: bisphenol A type epoxy resin, bisphenol F type epoxy resin or hydrogenated products thereof; diglycidyl phthalate and diglycidyl isophthalate , Diglycidyl terephthalate, glycidyl p-hydroxybenzoate, diglycidyl tetrahydrophthalate, diglycidyl succinate, diglycidyl adipate, diglycidyl sebacate , Triglycidyl trimellitate and other glycidyl epoxy resins; ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanedi Alcohol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, sorbitol poly Glycidyl ether epoxy resins such as glycidyl ether and polyglycidyl ether of polyglycerol; glycidyl amine epoxy resins such as triglycidyl isocyanurate and tetraglycidyl diaminodiphenylmethane; Epoxidized polybutadiene, epoxidized soybean oil and other linear aliphatic epoxy resins. In addition, novolac epoxy resins such as phenol novolac epoxy resin, o-cresol novolac epoxy resin, and bisphenol A novolac epoxy resin may also be used. Furthermore, brominated bisphenol A type epoxy resins, phosphorus-containing epoxy resins, epoxy resins containing dicyclopentadiene skeletons, epoxy resins containing naphthalene skeletons, anthracene type epoxy resins, tertiary epoxy resins, etc. can be used. Catechol, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, biphenyl type epoxy resin, bisphenol S type epoxy resin, etc.

環氧樹脂較佳為於一分子中具有2個以上之環氧基。其原因為，藉由與含羧基之苯乙烯系彈性體之反應而形成交聯構造，可展現較高之耐熱性。 The epoxy resin preferably has two or more epoxy groups in one molecule. The reason is that the cross-linked structure is formed by the reaction with the carboxyl group-containing styrene elastomer, which can exhibit high heat resistance.

含羧基之苯乙烯系彈性體可用以對硬化物(即導電性接著劑層)賦與所期望之介電特性(即高速傳送特性)而使用。含羧基之苯乙烯系彈性體，代表性者為將以共軛二烯化合物與芳香族乙烯基化合物之嵌段及無規構造為主體之共聚物、以及其氫化物經以不飽合羧酸改性者。作為芳香族乙烯基化合物，例如可列舉：苯乙烯、第三丁基苯乙烯、α-甲基苯乙烯、對甲基苯乙烯、二乙烯基苯、1,1-二苯基苯乙烯、N,N-二乙基-對胺基乙基苯乙烯、乙烯基甲苯、對第三丁基苯乙烯。又，作為共軛二烯化合物，例如可列舉：丁二烯、異戊二烯、1,3-戊二烯、2,3-二甲基-1,3-丁二烯等。 The carboxyl-containing styrene elastomer can be used to impart desired dielectric properties (ie, high-speed transmission characteristics) to the hardened product (ie, conductive adhesive layer). Carboxyl-containing styrenic elastomers are typically copolymers with a block and random structure of a conjugated diene compound and an aromatic vinyl compound as the main body, and its hydrogenated product is subjected to unsaturated carboxylic acid Modifier. As the aromatic vinyl compound, for example, styrene, tertiary butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N , N-Diethyl-p-aminoethyl styrene, vinyl toluene, p-tert-butyl styrene. Moreover, as a conjugated diene compound, butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, etc. are mentioned, for example.

含羧基之苯乙烯系彈性體之改性，例如可藉由於苯乙烯系彈性體之聚合時使不飽和羧酸共聚合而進行。又，亦可藉由於有機過氧化物之存在下將苯乙烯系彈性體與不飽和羧酸加熱、混練而進行。作為不飽和羧酸，例如可列舉：丙烯酸、甲基丙烯酸、馬來酸、伊康酸、富馬酸、馬來酸酐、伊康酸酐、富馬酸酐。藉由不飽和羧酸之改性量例如為0.1重量%~10重量%。 The modification of the carboxyl-containing styrene elastomer can be carried out, for example, by copolymerizing an unsaturated carboxylic acid during the polymerization of the styrene elastomer. In addition, it can also be performed by heating and kneading a styrene-based elastomer and an unsaturated carboxylic acid in the presence of an organic peroxide. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, maleic anhydride, itaconic anhydride, and fumaric anhydride. The amount of modification by the unsaturated carboxylic acid is, for example, 0.1% by weight to 10% by weight.

作為含羧基之苯乙烯系彈性體之具體例，可列舉將苯乙烯-丁二烯嵌段共聚物、苯乙烯-乙烯丙烯嵌段共聚物、苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-異戊二烯-苯乙烯嵌段共聚物、苯乙烯-乙烯丁烯-苯乙烯嵌段共聚物及苯乙烯-乙烯丙烯-苯乙烯嵌段共聚物等經以不飽和羧酸改性者。較佳為經以不飽和羧酸改性之苯乙烯-乙烯丙烯-苯乙烯嵌段共聚物。其原因為，與後述有機磷系阻燃劑之組合所產生之效果顯著，可非常良好地兼具優異之高速傳送特性(主要為低的比介電常數及介電損失正切)與優異之阻燃性。苯乙烯-乙烯丙烯-苯乙烯嵌段共聚物中之苯乙烯/乙烯丙烯之質量比，例如為10/90~90/10，較佳為10/90~50/50。質量比若於此範圍，可成為具有優異之介電特性之接著劑組成物。 As specific examples of carboxyl group-containing styrene elastomers, styrene-butadiene block copolymers, styrene-ethylene propylene block copolymers, styrene-butadiene-styrene block copolymers , Styrene-isoprene-styrene block copolymers, styrene-ethylene butene-styrene block copolymers and styrene-ethylene propylene-styrene block copolymers, etc. are modified with unsaturated carboxylic acid Sex. It is preferably a styrene-ethylene propylene-styrene block copolymer modified with an unsaturated carboxylic acid. The reason is that the combination with the organophosphorus flame retardant described below has a significant effect, and can very well combine excellent high-speed transmission characteristics (mainly low specific permittivity and dielectric loss tangent) and excellent resistance Flammability. The mass ratio of styrene/ethylene propylene in the styrene-ethylene propylene-styrene block copolymer is, for example, 10/90 to 90/10, preferably 10/90 to 50/50. If the mass ratio is within this range, it can become an adhesive composition with excellent dielectric properties.

含羧基之苯乙烯系彈性體之重量平均分子量Mw，較佳為1萬~50萬，更佳為3萬~30萬，尤佳為5萬~20萬。重量平均分子量Mw若於此範圍，可展現優異之接著性及介電特性。再者，於本說明書中，所謂重量平均分子量 Mw是將藉由凝膠滲透層析儀(以下亦稱為「GPC」)測定之分子量換算成苯乙烯之值。 The weight average molecular weight Mw of the carboxyl-containing styrene elastomer is preferably 10,000 to 500,000, more preferably 30,000 to 300,000, and particularly preferably 50,000 to 200,000. If the weight average molecular weight Mw is in this range, excellent adhesiveness and dielectric properties can be exhibited. Furthermore, in this specification, the so-called weight average molecular weight Mw is a value obtained by converting the molecular weight measured by a gel permeation chromatography (hereinafter also referred to as "GPC") into styrene.

樹脂成分中之環氧樹脂之調配量，相對於含羧基之苯乙烯系彈性體100重量份宜為1重量份~20重量份，較佳為3重量份~15重量份。 The blending amount of the epoxy resin in the resin component is preferably 1 part by weight to 20 parts by weight, preferably 3 parts by weight to 15 parts by weight relative to 100 parts by weight of the carboxyl-containing styrene elastomer.

除了環氧樹脂及含羧基之苯乙烯系彈性體外，樹脂成分亦可進而含有其他樹脂。作為其他樹脂，例如可列舉熱塑性樹脂。作為熱塑性樹脂之具體例，可列舉：苯氧樹脂、聚醯胺樹脂、聚酯樹脂、聚碳酸酯樹脂、聚伸苯醚樹脂、聚胺基甲酸酯樹脂、聚縮醛樹脂、聚乙烯系樹脂、聚丙烯系樹脂、聚乙烯基系樹脂。其他樹脂之種類及樹脂成分中之調配量，可根據目的或所期望之特性而適當地設定。 In addition to epoxy resin and carboxyl-containing styrene elastomer, the resin component may further contain other resins. Examples of other resins include thermoplastic resins. Specific examples of thermoplastic resins include: phenoxy resins, polyamide resins, polyester resins, polycarbonate resins, polyphenylene ether resins, polyurethane resins, polyacetal resins, and polyethylene resins. Resin, polypropylene resin, polyvinyl resin. The types of other resins and the blending amount of resin components can be appropriately set according to the purpose or desired characteristics.

有機磷系阻燃劑，代表性者為次膦酸(phosphinic acid)金屬鹽。作為次膦酸金屬鹽之具體例，可列舉：三-二乙基次膦酸鋁、三甲基乙基次膦酸鋁、三-二苯基次膦酸鋁、雙-二乙基次膦酸鋅、雙甲基乙基次膦酸鋅、雙-二苯基次膦酸鋅、雙-二乙基次膦酸氧鈦、四-二乙基次膦酸鈦、雙甲基乙基次膦酸氧鈦、四甲基乙基次膦酸鈦、雙-二苯基次膦酸氧鈦、四-二苯基次膦酸鈦。亦可使用次膦酸金屬鹽(例如有機次膦酸之鋁鹽)與多磷酸三聚氰胺之摻合物。次膦酸金屬鹽系阻燃劑有市售。作為市售之具體例，可列舉Clariant Japan公司製商品名「EXOLITE OP-930」、「EXOLITE OP-935」、「EXOLITE OP-1230」、「EXOLITE OP-1240」、「EXOLITE OP-1312」。 Organophosphorus flame retardants, the representative one is phosphinic acid (phosphinic acid) metal salt. Specific examples of phosphinic acid metal salts include: aluminum tris-diethylphosphinate, aluminum trimethylethylphosphinate, aluminum tris-diphenylphosphinate, and bis-diethylphosphinate Zinc acid, zinc bis-methyl ethyl phosphinate, zinc bis-diphenyl phosphinate, titanium oxide bis-diethyl phosphinate, titanium tetra-diethyl phosphinate, bis-methyl ethyl phosphinate Titanium phosphonate, titanium tetramethyl ethyl phosphinate, titanium bis-diphenyl phosphinate, titanium tetra-diphenyl phosphinate. It is also possible to use a blend of metal phosphinate (for example, aluminum salt of organic phosphinic acid) and melamine polyphosphate. A flame retardant based on metal phosphinate is commercially available. As specific examples on the market, Clariant Japan’s product names "EXOLITE OP-930", "EXOLITE OP-935", "EXOLITE OP-1230", and "EXOLITE OP-1240", "EXOLITE OP-1312".

導電性接著劑組成物中之有機磷系阻燃劑之調配量，相對於環氧樹脂及含羧基之苯乙烯系彈性體之合計100重量份，宜為10重量份~50重量份，較佳為15重量份~40重量份。藉由使用上述特定的樹脂成分且以上述量調配有機磷系阻燃劑，可賦與優異之阻燃性且實現優異之高速傳送特性。 The blending amount of the organic phosphorus flame retardant in the conductive adhesive composition is preferably 10 parts by weight to 50 parts by weight relative to 100 parts by weight of the total of epoxy resin and carboxyl-containing styrene elastomer It is 15 parts by weight to 40 parts by weight. By using the above specific resin component and blending the organic phosphorus flame retardant in the above amount, excellent flame retardancy can be imparted and excellent high-speed transmission characteristics can be achieved.

作為導電性填料，可使用任意之適當的導電性填料。作為導電性填料之具體例，可列舉：碳、銀、銅、鎳、焊料、鋁、對銅粉施以鍍銀之鍍銀銅填料、對樹脂球或玻璃珠等施以金屬鍍敷之填料。較佳為鍍銀銅填料或鎳。其原因為，較廉價且具有優異之導電性，且可靠性較高。導電性填料可單獨使用亦可組合二種以上使用。作為導電性填料之形狀，可視目的而採用任意之適當的形狀。作為具體例，可列舉：真球狀、小片狀、鱗片狀、板狀、樹枝狀、橢圓球狀、棒狀、針狀、不定形。 As the conductive filler, any appropriate conductive filler can be used. Specific examples of conductive fillers include: carbon, silver, copper, nickel, solder, aluminum, silver-plated copper fillers coated with silver on copper powder, fillers coated with metal plating on resin balls or glass beads, etc. . Preferably, it is silver-plated copper filler or nickel. The reason is that it is relatively inexpensive, has excellent conductivity, and has high reliability. The conductive filler may be used alone or in combination of two or more kinds. As the shape of the conductive filler, any appropriate shape can be adopted depending on the purpose. Specific examples include true spherical shape, small flake shape, scale shape, plate shape, dendritic shape, elliptical spherical shape, rod shape, needle shape, and amorphous shape.

導電性接著劑組成物中之導電性填料之調配量，相對於環氧樹脂及含羧基之苯乙烯系彈性體之合計100重量份，宜為10重量份~80重量份，較佳為20重量份~60重量份。若調配量過多，有印刷電路板對接地電路之接著性變得不足且不能獲得良好之傳送特性之情形。若調配量過少，則有導電性變得不足且不能獲得良好之屏蔽特性。 The compounding amount of the conductive filler in the conductive adhesive composition is preferably 10 parts by weight to 80 parts by weight, preferably 20 parts by weight relative to the total of 100 parts by weight of epoxy resin and carboxyl-containing styrene elastomer Parts ~ 60 parts by weight. If the amount is too much, the adhesion of the printed circuit board to the ground circuit may become insufficient and good transmission characteristics may not be obtained. If the blending amount is too small, the conductivity will become insufficient and good shielding characteristics cannot be obtained.

導電性接著劑組成物視目的亦可進一步含有任意之適當的添加劑。作為添加劑之具體例，可列舉：黏著 賦與劑、聚合起始劑、硬化促進劑、偶合劑、抗熱老化劑、調平劑、消泡劑、無機填充劑、顏料及溶劑。所加入之添加劑之數量、種類及調配量，可視目的或所期望之特性而適當地設定。 The conductive adhesive composition may further contain arbitrary appropriate additives depending on the purpose. Specific examples of additives include: Excipients, polymerization initiators, hardening accelerators, coupling agents, thermal aging agents, leveling agents, defoamers, inorganic fillers, pigments and solvents. The amount, type and blending amount of the additives added can be appropriately set depending on the purpose or desired characteristics.

導電性接著劑組成物可藉由任意之適當方法而硬化。作為硬化方法之代表例，可列舉熱壓。熱壓中之加熱溫度例如160℃~180℃，加壓壓力例如2MPa~5MPa，熱壓時間(硬化時間)例如30分鐘~60分鐘。 The conductive adhesive composition can be cured by any appropriate method. As a representative example of the hardening method, hot pressing can be cited. The heating temperature in the hot pressing is, for example, 160°C to 180°C, the pressing pressure is, for example, 2 MPa to 5 MPa, and the hot pressing time (hardening time) is, for example, 30 minutes to 60 minutes.

導電性接著劑層(導電性接著劑組成物之硬化物)之厚度宜為2μm~45μm，更佳為5μm~15μm。若為如此厚度，藉由與上述特定樹脂成分與有機磷系阻燃劑之組合所產生之效果及金屬層之厚度所產生之效果之相乘效果，於所獲得之屏蔽薄膜可兼具優異之高速傳送特性與阻燃性。 The thickness of the conductive adhesive layer (the cured product of the conductive adhesive composition) is preferably 2 μm to 45 μm, more preferably 5 μm to 15 μm. If it is such a thickness, the synergistic effect of the effect produced by the combination of the above-mentioned specific resin component and the organophosphorus flame retardant and the effect produced by the thickness of the metal layer can provide excellent shielding film. High-speed transmission characteristics and flame retardancy.

導電性接著劑層之比介電常數，於1GHz下宜為2.0~4.0，較佳為2.5~3.3，更佳為2.7~3.0。導電性接著劑層之介電損失正切於1GHz下宜為0.0015~0.0040，較佳為0.0015~0.0026。導電性接著劑層之阻燃性宜為VTM-0或較其良好。如此，可同時實現非常低之比介電常數及介電損失正切(結果為非常優異之高速傳送特性、尤其是高頻傳送特性)與優異之阻燃性為本發明之成果之一，此為藉由反覆修正及研究接著劑之樹脂成分、阻燃劑及各層之厚度與上述等特性之關係而初次獲得之未預期之優異效果。 The specific dielectric constant of the conductive adhesive layer is preferably 2.0 to 4.0 at 1 GHz, preferably 2.5 to 3.3, and more preferably 2.7 to 3.0. The dielectric loss tangent of the conductive adhesive layer is preferably 0.0015 to 0.0040 at 1 GHz, preferably 0.0015 to 0.0026. The flame retardancy of the conductive adhesive layer is preferably VTM-0 or better. In this way, it is one of the achievements of the present invention to achieve both a very low specific dielectric constant and a dielectric loss tangent (the result is very excellent high-speed transmission characteristics, especially high-frequency transmission characteristics) and excellent flame retardancy. By repeatedly modifying and studying the relationship between the resin composition of the adhesive, the flame retardant and the thickness of each layer and the above characteristics, the unexpected excellent effect was obtained for the first time.

C.保護層 C. Protective layer

保護層30代表性者為由任意之適當的樹脂薄膜構成。 所謂構成樹脂薄膜之樹脂，可為熱硬化性樹脂，亦可為熱塑性樹脂，亦可為電子束(例如可見光線、紫外線)硬化性樹脂。作為樹脂之具體例，可列舉：環氧樹脂、酚樹脂、醯胺樹脂、醇酸樹脂、胺基甲酸酯樹脂、(甲基)丙烯酸樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂。 The protective layer 30 is typically composed of any suitable resin film. The resin constituting the resin film may be a thermosetting resin, a thermoplastic resin, or an electron beam (for example, visible light, ultraviolet) curable resin. Specific examples of resins include epoxy resins, phenol resins, amide resins, alkyd resins, urethane resins, (meth)acrylic resins, polyimide resins, and polyimide resins. Resin.

保護層之厚度例如為1μm~10μm。 The thickness of the protective layer is, for example, 1 μm to 10 μm.

本發明之實施形態中之屏蔽薄膜，與印刷電路板貼合後，曝露於高溫(約270℃)之回焊步驟。因此，對於屏蔽薄膜中包含樹脂之構成要素、即保護層及導電性接著劑層亦要求能耐回焊步驟之耐熱性。於本發明之實施形態中，保護層及導電性接著劑層皆藉由具有上述構成而可滿足能耐回焊步驟之耐熱性。其結果，本發明之屏蔽薄膜整體可滿足能耐回焊步驟之耐熱性。 After the shielding film in the embodiment of the present invention is bonded to the printed circuit board, it is exposed to a high temperature (about 270°C) reflow step. Therefore, the protective layer and the conductive adhesive layer, which are the constituent elements containing the resin in the shielding film, are also required to be heat resistant to the reflow step. In the embodiment of the present invention, the protective layer and the conductive adhesive layer both have the above-mentioned structure to satisfy the heat resistance that can withstand the reflow step. As a result, the entire shielding film of the present invention can satisfy the heat resistance that can withstand the reflow step.

D.屏蔽印刷電路板 D. Shielded printed circuit board

本發明之實施形態中之屏蔽印刷電路板，包含印刷電路板與上述A項至C項所記載之屏蔽薄膜。印刷電路板具有形成有信號電路之基礎薄膜及覆蓋信號電路、設置於該基礎薄膜上之整個面之絕緣薄膜。於一個實施形態中，印刷電路板為軟性印刷電路板。屏蔽薄膜經由導電路接著劑層積層於印刷電路板之絕緣薄膜上。又，因為印刷電路板之構成為該業界所周知，故省略詳細說明。 The shielding printed circuit board in the embodiment of the present invention includes the printed circuit board and the shielding film described in the above items A to C. The printed circuit board has a base film on which a signal circuit is formed and an insulating film covering the entire surface of the signal circuit and arranged on the base film. In one embodiment, the printed circuit board is a flexible printed circuit board. The shielding film is laminated on the insulating film of the printed circuit board through the conductive circuit adhesive layer. In addition, since the structure of the printed circuit board is well known in the industry, detailed description is omitted.

[實施例] [Example]

以下，藉由實施例具體地說明本發明，但本發明並不限定於該等實施例。實施例中之評價項目如下所述。 又，於無特別載明之狀況下，實施例中之「份」及「%」為重量基準。 Hereinafter, the present invention will be specifically explained through examples, but the present invention is not limited to these examples. The evaluation items in the examples are as follows. In addition, if there is no special description, "parts" and "%" in the examples are based on weight.

(1)比介電常數及介電損失正切 (1) Specific permittivity and dielectric loss tangent

就實施例、參考例及比較例中製備之導電性接著劑組成物之硬化物，使用PNA-L網路分析儀N5230A(Agilent公司製)藉由共振腔微擾法(條件：23℃、1GHz)測定比介電常數(ε)及介電損失正切(tanδ)。 For the cured product of the conductive adhesive composition prepared in the Examples, Reference Examples and Comparative Examples, the PNA-L network analyzer N5230A (manufactured by Agilent) was used by the cavity perturbation method (conditions: 23°C, 1GHz) ) Determine the specific permittivity (ε) and the dielectric loss tangent (tanδ).

(2)阻燃性 (2) Flame retardancy

就實施例、參考例及比較例中製備之導電性接著劑組成物之硬化物，藉由依據UL94規格之VTM燃燒性試驗評價阻燃性。 Regarding the cured products of the conductive adhesive compositions prepared in the Examples, Reference Examples, and Comparative Examples, the flame retardancy was evaluated by the VTM flammability test in accordance with the UL94 standard.

(3)特性阻抗 (3) Characteristic impedance

關於實施例2及參考例1所獲得之屏蔽薄膜之特性阻抗，使用由示波器、TDR模組及TDR探針構成之系統進行評價。示波器使用Tektronix公司製之DSC8200。TDR模組使用Tektronix公司製之80E04。TDR探針使用Tektronix公司製之P8018(單端：50Ω)及P80318(差動：100Ω)。 The characteristic impedance of the shielding film obtained in Example 2 and Reference Example 1 was evaluated using a system composed of an oscilloscope, a TDR module, and a TDR probe. The oscilloscope uses DSC8200 manufactured by Tektronix. The TDR module uses 80E04 made by Tektronix. The TDR probe uses P8018 (single-ended: 50Ω) and P80318 (differential: 100Ω) manufactured by Tektronix.

(4)眼圖 (4) Eye diagram

關於實施例2及參考例1所獲得之屏蔽薄膜之眼圖(傳送波形)，使用由資料產生器、示波器及取樣模組構成之系統進行評價。示波器使用Tektronix公司製之DSC8200。資料產生器使用Agilent公司製之81133A。取樣模組使用Tektronix公司製之80E03。使位元率(bit rate)以0.5Gbps、1.0Gbps、2.0Gbps及3.0Gbps變化進行測定。 Regarding the eye patterns (transmission waveforms) of the shielding film obtained in Example 2 and Reference Example 1, a system composed of a data generator, an oscilloscope and a sampling module was used for evaluation. The oscilloscope uses DSC8200 manufactured by Tektronix. The data generator uses 81133A manufactured by Agilent. The sampling module uses 80E03 manufactured by Tektronix. The bit rate is measured at 0.5Gbps, 1.0Gbps, 2.0Gbps, and 3.0Gbps changes.

<實施例1> <Example 1>

於形成有離型層之剝離性薄膜上塗佈包含丙烯酸系樹脂之保護層用樹脂組成物，進行乾燥，藉此形成厚度5μm之保護層。接著，將藉由軋延加工而製作之厚度2μm之銅箔貼合於保護層。 A resin composition for a protective layer containing an acrylic resin was coated on the release film formed with the release layer, and dried to form a protective layer with a thickness of 5 μm. Next, a copper foil with a thickness of 2 μm produced by rolling is bonded to the protective layer.

接著，將以下所示之原料以以下所示之比例添加於附有攪拌裝置之1000ml燒瓶中，於室溫下攪拌6小時溶解，藉此製備固體成分濃度20%之液狀導電性接著劑組成物。將其使用刮刀(板狀之刮刀)塗佈於銅箔上，以100℃×3分鐘之條件進行乾燥，形成導電性接著劑層。再者，作為環氧樹脂使用甲酚酚醛型環氧樹脂(DIC公司製、EPICLON N-655-EXP)。作為含羧基之彈性體使用順丁烯二酸改性苯乙烯-乙烯丙烯-苯乙烯嵌段共聚物(Kuraray公司製、Septon2007)。作為有機磷系阻燃劑使用三-二乙基次膦酸鋁(Clariant Japan公司製、EXOLITE OP-935)。作為導電性填料使用樹枝狀之鍍銀銅粉(平均粒徑13μm)。 Next, add the following raw materials in the ratio shown below to a 1000ml flask equipped with a stirring device and stir at room temperature for 6 hours to dissolve, thereby preparing a liquid conductive adhesive composition with a solid content of 20% Things. This was coated on a copper foil using a doctor blade (a plate-shaped doctor blade), and dried under the conditions of 100° C.×3 minutes to form a conductive adhesive layer. In addition, as the epoxy resin, a cresol novolac epoxy resin (manufactured by DIC Corporation, EPICLON N-655-EXP) was used. As the carboxyl group-containing elastomer, a maleic acid modified styrene-ethylene propylene-styrene block copolymer (manufactured by Kuraray, Septon 2007) was used. As the organic phosphorus flame retardant, aluminum tris-diethylphosphinate (manufactured by Clariant Japan, EXOLITE OP-935) was used. As the conductive filler, dendritic silver-plated copper powder (average particle size 13μm) was used.

環氧樹脂：10份 Epoxy resin: 10 parts

含羧基之彈性體：100份 Carboxyl-containing elastomer: 100 parts

有機磷系阻燃劑：30份 Organic phosphorus flame retardant: 30 parts

導電性填料：20份 Conductive filler: 20 parts

咪唑系硬化促進劑(四國化成公司製、Curezol C11-Z)：0.2重量份 Imidazole-based hardening accelerator (manufactured by Shikoku Chemical Co., Curezol C11-Z): 0.2 parts by weight

溶劑(甲苯/甲基乙基酮=90：10質量比)：400重量份 Solvent (toluene/methyl ethyl ketone=90:10 mass ratio): 400 parts by weight

如上所述，製成具有金屬層/導電性接著劑層之構成之 屏蔽薄膜。將所獲得之屏蔽薄膜進行上述(1)~(2)評價。將結果顯示於表1。 As mentioned above, a metal layer/conductive adhesive layer is made Shielding film. The obtained shielding film was evaluated in (1) to (2) above. The results are shown in Table 1.

<實施例2> <Example 2>

除了使用厚度為5.5μm之銅箔外，以與實施例1相同方法獲得屏蔽薄膜。將所獲得之屏蔽薄膜進行上述(1)~(4)評價。將比介電常數、介電損失正切及阻燃性之結果顯示於表1。將特性阻抗之結果與參考例1之結果一併顯示於圖2。將眼圖之結果與參考例1及比較例6之結果一併顯示於圖3。 A shielding film was obtained in the same manner as in Example 1, except that a copper foil with a thickness of 5.5 μm was used. The obtained shielding film was subjected to the above-mentioned (1) to (4) evaluation. Table 1 shows the results of specific permittivity, dielectric loss tangent, and flame retardancy. The result of characteristic impedance and the result of Reference Example 1 are shown in Figure 2. The results of the eye diagram and the results of Reference Example 1 and Comparative Example 6 are shown in FIG. 3.

<實施例3> <Example 3>

除了有機磷系阻燃劑之添加量如表1所示外，以與實施例2相同方法獲得屏蔽薄膜。將所獲得之屏蔽薄膜進行上述(1)~(4)評價。將比介電常數、介電損失正切及阻燃性之結果顯示於表1。 Except for the addition amount of the organic phosphorus flame retardant as shown in Table 1, the shielding film was obtained in the same manner as in Example 2. The obtained shielding film was subjected to the above-mentioned (1) to (4) evaluation. Table 1 shows the results of specific permittivity, dielectric loss tangent, and flame retardancy.

<實施例4> <Example 4>

除了有機磷系阻燃劑之添加量如表1所示外，以與實施例2相同方法獲得屏蔽薄膜。將所獲得之屏蔽薄膜進行上述(1)~(4)評價。將比介電常數、介電損失正切及阻燃性之結果顯示於表1。 Except for the addition amount of the organic phosphorus flame retardant as shown in Table 1, the shielding film was obtained in the same manner as in Example 2. The obtained shielding film was subjected to the above-mentioned (1) to (4) evaluation. Table 1 shows the results of specific permittivity, dielectric loss tangent, and flame retardancy.

<實施例5> <Example 5>

除了有機磷系阻燃劑及導電性填料之添加量如表1所示外，以與實施例2相同方法獲得屏蔽薄膜。將所獲得之屏蔽薄膜進行上述(1)~(4)評價。將比介電常數、介電損失正切及阻燃性之結果顯示於表1。 Except that the addition amount of the organic phosphorus flame retardant and the conductive filler is as shown in Table 1, the shielding film was obtained in the same manner as in Example 2. The obtained shielding film was subjected to the above-mentioned (1) to (4) evaluation. Table 1 shows the results of specific permittivity, dielectric loss tangent, and flame retardancy.

<參考例1> <Reference example 1>

除了未使用阻燃劑外，以與實施例1相同方法獲得屏蔽薄膜。將所獲得之屏蔽薄膜進行上述(1)~(4)評價。將比介電常數、介電損失正切及阻燃性之結果顯示於表1。將特性阻抗之結果與實施例2之結果一併顯示於圖2。將眼圖之結果與實施例2及比較例6之結果一併顯示於圖3。 A shielding film was obtained in the same manner as in Example 1 except that no flame retardant was used. The obtained shielding film was subjected to the above-mentioned (1) to (4) evaluation. Table 1 shows the results of specific permittivity, dielectric loss tangent, and flame retardancy. The result of characteristic impedance and the result of Example 2 are shown in FIG. 2 together. The results of the eye diagram and the results of Example 2 and Comparative Example 6 are shown in FIG. 3 together.

<比較例1> <Comparative Example 1>

除了取代有機磷系阻燃劑30份，使用氮系阻燃劑(氰尿酸三聚氰胺、日產化學公司製、MC-4500)30份外，以與實施例1相同方法獲得屏蔽薄膜。將所獲得之屏蔽薄膜進行上述(1)~(2)評價。將結果顯示於表1。 Except for replacing 30 parts of the organophosphorus flame retardant and using 30 parts of a nitrogen flame retardant (melamine cyanurate, manufactured by Nissan Chemical Co., MC-4500), a shielding film was obtained in the same manner as in Example 1. The obtained shielding film was evaluated in (1) to (2) above. The results are shown in Table 1.

<比較例2> <Comparative Example 2>

除了作為樹脂成分使用改性環氧樹脂(丙烯酸改性環氧樹脂、日本化藥公司製、ZCR-1798H)外，以與實施例1相同方法獲得屏蔽薄膜。將所獲得之屏蔽薄膜進行上述(1)~(2)評價。將結果顯示於表1。 Except for using a modified epoxy resin (acrylic modified epoxy resin, manufactured by Nippon Kayaku Co., Ltd., ZCR-1798H) as the resin component, a shielding film was obtained in the same manner as in Example 1. The obtained shielding film was evaluated in (1) to (2) above. The results are shown in Table 1.

<比較例3> <Comparative Example 3>

除了蒸鍍銀形成金屬層(厚度0.1μm)、作為樹脂成分使用含磷之環氧樹脂(新日鐵化學公司製、FX-305BEK)、將導電性接著劑層之厚度設為10μm、以及使用氮系阻燃劑外，以與實施例1相同方法獲得屏蔽薄膜。將所獲得之屏蔽薄膜進行上述(1)~(2)評價。將結果顯示於表1。 In addition to vapor deposition of silver to form a metal layer (thickness 0.1μm), use of phosphorus-containing epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., FX-305BEK) as a resin component, set the thickness of the conductive adhesive layer to 10μm, and use Except for the nitrogen-based flame retardant, a shielding film was obtained in the same manner as in Example 1. The obtained shielding film was evaluated in (1) to (2) above. The results are shown in Table 1.

<比較例4> <Comparative Example 4>

除了有機磷系阻燃劑之添加量如表1所示外，以與實施例2相同方法獲得屏蔽薄膜。將所獲得之屏蔽薄膜進行上述 (1)~(4)評價。將比介電常數、介電損失正切及阻燃性之結果顯示於表1。 Except for the addition amount of the organic phosphorus flame retardant as shown in Table 1, the shielding film was obtained in the same manner as in Example 2. The obtained shielding film is subjected to the above (1)~(4) Evaluation. Table 1 shows the results of specific permittivity, dielectric loss tangent, and flame retardancy.

<比較例5> <Comparative Example 5>

除了有機磷系阻燃劑之添加量如表1所示外，以與實施例2相同方法獲得屏蔽薄膜。將所獲得之屏蔽薄膜進行上述(1)~(4)評價。將比介電常數、介電損失正切及阻燃性之結果顯示於表1。 Except for the addition amount of the organic phosphorus flame retardant as shown in Table 1, the shielding film was obtained in the same manner as in Example 2. The obtained shielding film was subjected to the above-mentioned (1) to (4) evaluation. Table 1 shows the results of specific permittivity, dielectric loss tangent, and flame retardancy.

<比較例6> <Comparative Example 6>

除了有機磷系阻燃劑及導電性填料之添加量如表1所示外，以與實施例2相同方法獲得屏蔽薄膜。將所獲得之屏蔽薄膜進行上述(1)~(4)評價。將比介電常數、介電損失正切及阻燃性之結果顯示於表1。將眼圖之結果與實施例2及參考例1之結果一併顯示於圖3。 Except that the addition amount of the organic phosphorus flame retardant and the conductive filler is as shown in Table 1, the shielding film was obtained in the same manner as in Example 2. The obtained shielding film was subjected to the above-mentioned (1) to (4) evaluation. Table 1 shows the results of specific permittivity, dielectric loss tangent, and flame retardancy. The results of the eye diagram are shown in FIG. 3 together with the results of Example 2 and Reference Example 1.

Figure 105116308-A0202-12-0017-1
Figure 105116308-A0202-12-0017-1

<評價> <evaluation>

由表1可知，藉由於屏蔽薄膜之導電性接著劑層中組合使用特定之樹脂成分、特定量之有機磷系阻燃劑與特定量之導電性填料，可賦與優異之阻燃性且可實現非常低之比介電常數及介電損失正切(即優異之高速傳送特性)。又，如圖2所示，可知實施例2之屏蔽薄膜與參考例1之屏蔽薄膜相比，阻抗變化較小。進而，如圖3所示，可知實施例2之屏蔽薄膜與參考例1及比較例6之屏蔽薄膜相比，眼圖較優異(尤其是位元率越大越明顯)。即，圖2及圖3明確顯示藉由於屏蔽薄膜之導電性接著劑層中於特定之樹脂成分中添加有機磷系阻燃劑，不僅阻燃性、傳送特性亦明顯改善。此是藉由組合特定之樹脂成分與有機磷系阻燃劑之未預期之優異效果。 It can be seen from Table 1 that the combination of a specific resin component, a specific amount of organic phosphorus flame retardant and a specific amount of conductive filler in the conductive adhesive layer of the shielding film can impart excellent flame retardancy and Achieve very low specific dielectric constant and dielectric loss tangent (that is, excellent high-speed transmission characteristics). Furthermore, as shown in FIG. 2, it can be seen that the shielding film of Example 2 has a smaller impedance change than the shielding film of Reference Example 1. Furthermore, as shown in FIG. 3, it can be seen that the masking film of Example 2 has better eye patterns than the masking films of Reference Example 1 and Comparative Example 6 (especially the higher the bit rate, the more pronounced). That is, FIGS. 2 and 3 clearly show that by adding an organic phosphorus flame retardant to a specific resin component in the conductive adhesive layer of the shielding film, not only the flame retardancy and transmission characteristics are significantly improved. This is the unexpected excellent effect of combining specific resin components and organic phosphorus flame retardants.

產業上之可利用性 Industrial availability

根據本發明之實施形態之屏蔽薄膜，可適合用作印刷電路板之電磁波屏蔽薄膜。 The shielding film according to the embodiment of the present invention can be suitably used as an electromagnetic wave shielding film for printed circuit boards.

10‧‧‧金屬層 10‧‧‧Metal layer

20‧‧‧導電性接著劑層 20‧‧‧Conductive adhesive layer

30‧‧‧保護層 30‧‧‧Protection layer

40‧‧‧離型薄膜 40‧‧‧Release film

100‧‧‧屏蔽薄膜 100‧‧‧Shielding film

Claims (5)

一種屏蔽薄膜，具備金屬層、及配置於該金屬層之一側之導電性接著劑層；該導電性接著劑層包含環氧樹脂與含羧基之彈性體之硬化物、有機磷系阻燃劑及導電性填料；該金屬層之厚度為0.3μm~7μm；構成該導電性接著劑層之導電性接著劑，相對於該環氧樹脂及該含羧基之彈性體合計100重量份，含有10重量份~50重量份之該有機磷系阻燃劑、及10重量份~80重量份之該導電性填料。 A shielding film is provided with a metal layer and a conductive adhesive layer arranged on one side of the metal layer; the conductive adhesive layer includes a cured product of an epoxy resin and an elastomer containing a carboxyl group, and an organic phosphorus flame retardant And conductive filler; the thickness of the metal layer is 0.3μm~7μm; the conductive adhesive constituting the conductive adhesive layer contains 10 parts by weight relative to the total 100 parts by weight of the epoxy resin and the carboxyl group-containing elastomer 50 parts by weight of the organophosphorus flame retardant, and 10 parts by weight to 80 parts by weight of the conductive filler. 如請求項1之屏蔽薄膜，其中前述含羧基之彈性體為經以不飽和羧酸改性之苯乙烯-乙烯丙烯-苯乙烯共聚物。 The shielding film of claim 1, wherein the aforementioned carboxyl group-containing elastomer is a styrene-ethylene propylene-styrene copolymer modified with an unsaturated carboxylic acid. 如請求項1或2之屏蔽薄膜，其中前述有機磷系阻燃劑為次膦酸金屬鹽。 The shielding film of claim 1 or 2, wherein the aforementioned organic phosphorus flame retardant is a metal salt of phosphinic acid. 如請求項1或2之屏蔽薄膜，其中前述導電性接著劑層具有VTM-0或較其良好之阻燃性，且於1GHz下具有2.0~4.0之比介電常數及0.0015~0.0040之介電損失正切。 The shielding film of claim 1 or 2, wherein the aforementioned conductive adhesive layer has VTM-0 or better flame retardancy, and has a specific dielectric constant of 2.0 to 4.0 and a dielectric constant of 0.0015 to 0.0040 at 1 GHz Loss tangent. 一種屏蔽印刷電路板，包含如請求項1至4中任一項之屏蔽薄膜。 A shielding printed circuit board comprising the shielding film according to any one of claims 1 to 4.
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US10196545B2 (en) 2019-02-05
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JP6534442B2 (en) 2019-06-26

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